Chrysene derivatives and process of making same



Patented Feb." 3,

(desired; "-niore than one mole of 'fthe same for Y Walter Kern, Sissach, andRichardToblcr, Ric.- Phen switzerlandgassi gporsito society of Qhem l llnd ilstr -yi n laaslefBasel,Switzerland I This ;invention.1;relates:itdithe manutacture of derivativesof chrysenezrbyicausingia:h'alogenisuba stitution product of the chrysene .to reactvwith a compound which contains-at least onehydrogen atom attached vtonitrogen and a group capable 'of,.'.being' vatted'. I, f" f ["For'therea'c on withthe halogen substi bro'du' tof "chrysengj forlinstance Z- -bIOIIlQ- I l 'dibrorno or 12,2l8-diCh161QChIIYSEI16 which "rnay contain other substituents besides halogen, there 4 maybe used ivarious compounds containing at least one h dlf nf atom attachedfto nitrogen and-f'a group capable of being 'vatted, and; tfif diflferent -'pmpoimgs of this' ki'nwmay be causcd: :15 to{react "simultaneously or succ essive-ly on chrysen cor' tainir1g more than i onej; halogen atom." Gompounds which contain at leg" "6 hydrogen -'atorn"attaphed to nitrogen and a capable 55f being"vatt'egl; for instancea cf icl bound carbonylgroupymay-b anfth non derivatiye's 01" they may belo g ft V a 'soiv'ent-cr- Y diluent, for instance nitrobenaene, chloronaphthalene or amyl alcohol, preferably in'the pre senceof a catalyst, for instance copper or copper compound, as; well as or an. acidbinding highly condensed ring.systems; such conipo as agent, for instancefariyalkali carbonate, and/or are; for exainple, --'amino 8lnthraj 'l dehydrated 'sQdiumQace tate; I

instance l-amino-anthraquinone ana i-ammd-m Theproducts loflthe invcntion are especiallyarylaminoanthraquinones, amino-,acylamino-an- C valuable intermediatef'iaroducts for the manufac thraquinones, wherein thejacyl residues may be, ture of dyestuffs;

no-anthraquinone; amino-pyranthrones, aminoanthanthrones, 'aminoperylenequinones, amino- 7 01d, dianthrones, amino N-dihydro-anthraqumoneg azines, amino-anthraquinone-azines, aminobenzheterocyclic ring, for instance amino-1:9-an-f for instance, the residue of an aliphatic, aro- The following exarnplg'illustrate, the inven matic or heterocyclic acid, for instance carboxylic x th rt being byfwight unless therwise acids, for example 1,-amino- 4-benzoy1amino- 30 t t nd the; relationship; offthe partsby vola q one; m r"5 benzoyla n -a 1 ume wpartsby wightis that which exists bethraquinone, 1 amino-5-benzoylamino-8emeth we the litre jh gh' i1' oxyanthraquinone, 1-amino-5z8fdibenzoylamino Y 1 V anthraquinone; 1 amino-anthraquinonoyl-ami pyrenequinones, aminoflavanthrenes, aminodi- V benzanthrones; amino-anthraquinone derivatives L in which the 1- and9-positions are members ofa thrapyrimidines, amino -:1 9 -'anthrapyridones, amino-1 9-isQthiazo1e-anthrones and amino;- 1 :9-v pyrazole-anthrones; -finally amino-anthraquinone derivatives in which two carbon atoms in ortho-position to each other are -members' of a heterocyclicl ringysystem for -.instance-amino:"1i22-" anthraguinone-acridones. All. these. Qompoumis may contain substitufin i; Determination;ofinitrogen:

Examplerz 10.3 parts of 2-bromoehrysene made by monobrominating chrys'ene in nitr0benzene,' 6 parts of anhydrous sodium acetate, 7.5 parts of l-arriino-anthraquinone and 1.6 parts of cuprous chloride are suspended in 145 parts'of nitrobenzene and the wholelis heated for 20 hours at 190-200 C. After cooling, the mixture is filtered and the solid matter washed with nitrobenzene and benzene and then extracted with boiling hydrochloric acid of 1 per cent strength for purification. Red needles are obtained in good yield; they may be recrystallized from nitrobenzene and then melt at 280-285" C. They' color concen trated sulfuric acid brown. Analysis shows them to be a 1'-(anthraquinonyl)2aminochrysene of theformula Example 3 10.3 parts of Z-bromochrysene, made by monobrominating chrysene in nitrobenzene, 12 parts of l-amino-4-benzoylamino-anthraquinone, 1,6- parts of cuprous chloride and 6 parts of anhydrous sodium acetate are suspended in 145 parts of nitrobenzene and the whole is stirred for 20 hours at a temperature of 190-200 C. After cooling and filtering, the solid matter is Washed and extracted with boiling dilute hydrochloric acid for removing copper compounds. This condensation product obtained in very good yield can be recrystallized from nitrobenzene to form blue needles which dissolve in concentrated sulfuric acid to a brown-yellow solution, decompose at 340-350" C. and can be vatted with difliculty.

The product is (4-benzoylamino-anthraquinonyl-1'-) -2-aminochrysene of the formula When 2-bromo'chrysene is condensed with 1- 'amino-5-benzoy1amino-anthraquinone there is obtained (5' benzoylamino anthraquinonyl 1-')-2-aminochrysene, a brown crystalline powder which dissolves in concentrated sulfuric acid to a brown solution.

A similar product is obtained by using 2- bromo-8-nitrochrysene instead of 2-bromochrysene. 1

Example 4 18 parts of anhydrous sodium acetate and 18 parts of calcined sodium carbonate are together heated to boiling with 480 parts of nitrobenzene until 30 parts of nitrobenzene have distilled. After cooling to 190200 C. (oilbath temperature) 23.2 parts of 2:8-dibromochrysene,' 42 parts of 1 amino 4 benzoylamino-anthraqui none and 1.5 parts of cuprous chloride areadded and the whole is stirred at the said temperature for16 hours. It is then vfiltered 'hot and the solid matter is washed with 'nitrobenzene, benzene and alcohol and extracted with boiling dilute hydrochloric acid for purification; it is filtered, washed and dried. There is obtained in very good yield (above per cent) a blue powder which colors concentrated sulfuric acid brownyellow, melts at above 460 C. and is vatted with great difficulty. Analysis shows it to be di-(4-; benzoyl -amino 1' anthraquinonyl) -2:8-diaminochrysene of the formula com-0 O-NH c") The same product is obtained by substituting for the 2:8-dibromochrysene an equivalent quan; tity of 2:8-dichlorochrysene 7 (2) Condensation product from 1 2 incl 2:8dibroinochryscne.

. blue;

(3) Condensation product from 1 2 mol l-amino-4-anilinoanmoi 2:8-dibromochrysene. thraqumone. Blue-violet needles. H2804 conc.: blue.

(4) Condensation product from 1 2 mol 1-amino-3-(N)4;benzmo12z8-dibromochrysene. anthraquinone condone.

Green powder. H2804 conc.:

black-violet-grcy.

(5) Condensation product from 1 2 mol 1:4-diamlnoanthraquimol 2:8-dibron1ochrysenc. none. Blue-black powder.

H2804 conc.: blue.

Example 8 9 parts of anhydrous sodium acetate and 9 parts of calcined sodium carbonate are heated to boiling with 480 parts of nitrobenzene until 48 parts of nitrobenzene have distilled. After cooling to 160--165 0., 23.2 parts of 2:8-dibromochrysene obtained by dibrominating chrysene in nitrobenzene, 21 parts of 1-amino-4-benzoylamino-anthraquinone, 0.75 part of cuprous chloride are added and the mixture is stirred for 16 hours at 160-165 C. It is now filtered hot, the solid matter washed with nitrobenzene, benzene and alcohol, and for purification extracted with boiling dilute hydrochloric acid. It is filtered, washed and extracted several times with alcohol. After recrystallization from a-chloronaphthalene there is obtained a good yield of small blue needles of the formula NHC o"c6H5 soluble in concentrated sulfuric acid to a greenlsh yellow solution which soon becomes brownolive and decomposes at 380C.

Eran mole 9 (I) NE-C O-CeHi 5-benzoylamino-anthraquinone and 0.3 part of cuprous chloride are added and the mixture is stirred for 16 hours at the said temperature. It is now filtered hot, the solid matter is washed with nitrobenzene, benzene and alcohol, and then purified by extraction With'boiling dilute hydrochloric acid, filtered, washed with water and dried. A brown-blue powder is thus obtained in very good yield. It may be recrystallized from a-chloronaphthalene; it decomposes at 434 C. and colors concentrated sulfuric acid brown. Analysis shows it to be a (5'-benzoylamino-1'- NH--C oo.H.

Example 1 0 11 parts of a tetrabromochrysene, 28 parts of 1 amino e 4 benzoylamino anthraquinone, 12 parts of 'calcined sodium carbonate, 12 parts of anhydrous sodium acetate and 1 part of cuprous chloride are suspended in 480 parts of nitrobenzene and the mixture is kept at 190-200 C. for 16 hours. It is then filtered hot and the solid matter extracted with boiling nitrobenzene, then again filtered, washed and extracted with boiling dilute hydrochloric acid to purify it. There is thus obtained in good yield a blackgreen powder which dissolves in concentrated sulfuric acid to an olive-green solution; it melts at above 460 C. and dyes cotton in a red-brown vat grey-green tints.

If instead of 1-amino-4-benzoylamino-anthraquinone there is used 1-amino-5-benzoylaminoanthraquinone one obtains a brownish black product which dissolves in concentrated sulfuric acid to an olive brown solution and decomposes at above 460 C.

The tetrabromochrysene used in this example may be made as follows:

45.6 parts of chrysene are suspended in 400 parts of nitrobenzene, some iodine is added and in the course of 8 hours 280 parts of bromine are added by drops at 15-25 C. The whole is then stirred for 16 hours at 25-30 C. and then for 24 hours at 35-40 0., followed by one hour at 50-60 C. and finally one hour at 115-120 C. By this time the product has separated and filtered at C., washed and dried. After two recrystallisations from nitrobenzene colorless needles are obtained which melt at above 300 C. and contain 59 .per cent of bromine corresponding with a tetrabromochrysene.

A similar brominated chrysene is obtained by brominating dibromochrysene in a concentrated sulfuric acid solution in the presence of iodine.

A product similar tothat described in paragraph 1 of this example is obtained when a more highly brominated chrysene is used which has been made in the following manner:

36.8 parts of 2.8-dibromochrysene obtainable by dibrominating chrysene in nitrobenzene are suspended in 400 parts .of nitrobenzene, some iodine is added and there are added to the mixthree by drops 1'08 parts of bromine'-in tlie1course of 8 hours at C. Stirring is first conducted; for 16 hours at -30 0., whereupon the tem'- perature is raised by stages, namely 24 hours 'at '35-40 C. and one hour: eachat 60 0.115-

120 C. and 190 C. After cooling to C., the whole is filtered by suction and the solid matter is washed, whereby white needles'are obtained which after recrystallisation, from nitrobenzene melt at 345 C.

Example 11 9 parts of anhydrous sodium acetate, 9 parts of calcined sodiumcarbonategand 480 parts of nitrobenzene are heated together to boiling until 48 parts of nitrobenzene have distilled. After cooling to 160-165 C. there are added 23.2 parts of 2:,8-dibromochrysene obtained by dibrominating. chrysene in nitrobenzene, 20.6 parts of 1- amino-5-benzoylamino-anthraquinone and 0.75 part of cuprous' chlorideyand the mixture is stirred for 16 hours at 160-165 C. After filter ing hot the-solid matter is: washed withnitrobenzene, benzene and alcohol and is extracted with boiling dilute hydrochloric acid to purify it, finally filterech. washed and again extracted with alcohol. Brown olive needles of the forare obtained in good yields? they issolvser in concentrated sulfuric acid to a brown solution and melt at above 3.009., C.

v Example r 1.5 parts of anhydrous sodium acetate, 1.5 parts of calcined sodium carbonatei and 120 parts of nitrobenzene are heated together to boiling until 12 parts of nitrobenzene have distilled. After cooling to 193-200 0., 6.5.1 parts of the product 208% '-m1e-5mas'sis:; filtredhotzand Lthe: solidi matter -weshed2':.witih nitrobenzene; benzene; and;

alcohol and extracted with boiling dilute mama chloniciacid ior-ipurificationigthem filteredtwaslied andiidrie .vlTl erek-i's obtained imgQ0d"fyiE1d as rediebrowinlpowdenvofixther comma.

' 0 NH-O o-Qokm'e soluble in concentrated sulfuricacid to a brown solution and melting at aitemperature above I I I Example. 15L I 1.95 parts of 2z8-dibroniochrysene, 3.9 parts of 1 amino-5+(para-chl0ro)-benzoylamino anthraquinone, 1.5 parts of anhydrous sodium 'facetate, 1.5 parts of calcinemsodium carbonate and 0.15 'part of cuprous chloride are suspended in 60 parts of dry nitrobenzene and the mixture is stirred for 18 hoursat a temperature of 193-209 C. The mass is then filteredhot and the solid matter fwashedi with nitrobenzene, benzene and alcohol, and extracted with L boiling dilute hydrochloric acid for purification; it is then filtered, washed and dried." There is obtained in good yieldya'darkbrown powder of the formula. V

obtained as described in Example 11, 3.5 partsof amino-5-benzoylamino-anthraquinone and 0.15 part of cuprous chloride are added and themixture is stirred for 16. hours alien; external temperature of 194-204 C. After filtering hot,'the

solid matter is washed! with nitrobenzene, benzene and alcohol and for purification extracted 7 with boiling dilute hydrochloric acid; filtered, washed and again extracted with boiling alcohol. There is obtained ineyeryggood yield the (ii-(5,- benzoylamino-1-anthraquinonyl) -2 8 diaminochrysene described in Example 5.

Example 1 3 1.95 parts of 2:8.-dibromochrysene, 3.85 parts of 1 amino 5 (para methoxy-benzoylaminoe anthraquinone, 1.5 parts of anhydrous sodium aifietatfig parts; of: calcinedrsodium; carbonate aud0;15ipamti:ofi cuprousachloride are suspended incfiocpartsteffidnyz-nitrobenzeneand-the.mixture is sth rd for- 1'8rhours1'ati antemperatureeiofi 193 soluble in concentrated sulfuric'acid to a brown solution and melting at a temperature above 460Ci'-' A similar condensation product is obtained if in place of the 1-amino-5-(para-chloro)-benzoylamino-anthraquinone there is used l-amino- 5-(ortho-chloro) -benzoylamino anthraquinone or I-amino-S-(meta-chloro)-benzoylamino anthraquinone.

Example 15 3 parts of anhydrous sodium acetate, 3 parts of calcined sodium carbonate and 96 parts of nitrobenzene are together heated to boiling until 12 parts of nitrobenzene have distilled. After cooling to 193203 C. (oil bath temperature) 3.9 parts of 2:8-dibromochrysene, 5.8 parts of 1- amino-5-acetylamino-anthraquinone and 0.26 part of cuprous chloride are added and the whole is stirred for 18 hours at the said temperature. After hot filtration the solidmatter is washed with nitrobenzene, benzene and alcohol, and for purification extracted with boiling dilute hydrochloric acid and then filtered, washed and dried. There are obtained in very good yield brown-olive needles of the formula NH-O O-CH:

which dissolve in concentrated sulfuric acid to a red solution and melt at a temperature above Example 16 1.5 parts of anhydrous sodium acetate, 1.5 parts of calcined sodium carbonate and 72 parts of nitrobenzene are together heated to boiling until 12 parts of nitrobenzene are distilled. After cooling to 190-200 C. (oil bath temperature) there are added 1.95 parts of 2'8-dibromochrysene, 2.6 parts of -amino-1:9-anthrapyrimidine and 0.15 part of cuprous chloride. The whole is stirred for 24 hours at a temperature of 196206 C. and then filtered hot. The solid matter is washed with nitrobenzene, benzene and alcohol, and for purification extracted with boiling dilute hydrochloric acid, then filtered, washed and again extracted with boiling alcohol. There is obtained in very good yield an olive-brown crystalline powder of the formula CH lTIN which colors concentrated sulfuric acid brownolive, melts at a temperature above 460 C. and dyes cotton grey-green tints in a brown vat.

Example 17 3 parts of anhydrous sodium acetate, 3 parts of calcined sodium carbonate and parts of nitrobenzene are heated together to boiling until 12 parts of nitrobenzene have distilled. After cooling to -200 C., 3.86 parts of 2:8-dibromochrysene, 5.7 parts of 4-amino-N-methyl-1t9- anthrapyrldone and 0.3 part of cuprous chloride are added and the mass is stirred for 24 hours at 196-206 C. After filtering hot the solid matter is washed and extracted with boiling dilute hydrochloric acid for purification; it is then filtered, washed and dried. A brown crystalline powder of the formula /C0 CHz-N EH is thus obtained in good yield; it colors concentrated sulfuric acid violet and melts at a temperature above 460 C. Analysis shows it to be a condensation product from 1 mol 2l:.8-dibromozmzzgozm e I chrysene and 2 mols 4-amino-Nernethyli-ltzi9i ansolubleziinfi eonentrfitdl sulfurio ;cidto red' 'thmpyridone; solution. I L x a Exqmplefill T The condensation of l rmol ,2.v dibromochrynitrob enzenei haveedistilledf .After ooollngl to "7.6 parts of 1-amino-5'cinn.moylamli1o-anthre l v qulnone= there: isrobtainedtan olive-r-broymrpgyldel;

'oftheformula. Iv

. alipar tsof calcined sodinm, carbonate az me 5 0110571) amino antfimqfimbfig 7 yields a I brown of anhydrous sodiumaoetete and 3108'; po nt 01ml; trobe'nzeneare together :boiled -until l2wpantsnoipowderof the formula I 193-203 0., 3.86 par-ts m: ziambromocm se ei' quinone and 0-;3"part oL- epprous ehloride are' de nd h i u is: tir eea h w e e nem neei 241mm T e id mettemsefll tered hot wa-shed andextracted: lilrith boiling dl-L lute hydrochloric,acid"fo epurification then:fil v ten-ed,- twashed. andfirextrected withtboiling eohol Acbnown powder ottheiorinulgs v a am; admin dnnentiiefiesumune iacidibrown red anili'dyesfcottomolwel-browmtintsfin aubrown e "watt r t iszthus obteinedu in goodiyieljd twhlc'lndlssolves in concentrated sulfuric acidstoa momngsoliition, e in When; lpm'ol 2: 8edibromophrysene licondensed with 221110151 l-amino.-. 5 i8, -pyrsidoyleni anthrax.-

-throne, 1.95 parts of 2:8-dibroinochrysenef15 parts-each of anhydrpu'ssod'ium acetate and cal cined'sodium carbonate and 0.2 part ofcuprous chloride are suspended inj120parts of nitroben zene and the mixtur'ls kept at a. temperature I of 208-212" C. for 2211011151. It is then filtered dilute hydrochloric acid for jpufrification. A black powderls thus obtained in good gvield. It dis- ,esolves .in concentratedsulfuricW-alcid to a, reddyes cotton fast greenish grey tints in a blue vat- Emam le 2o 9.7 parts of (4 5-ben'zoy1a1hino anthraquinonyl)e- 1':2-amino 8-brombchrysene obtained as deg scribed in Example 8,169 gpartspf l-amino l anilino-anthraqilin'ong 2.5 parts of anhydrous sodium acetate,'2. 5 parts or c'aJcined sodium c'arbonate and 0.3vpart of cuprouschloride are sus pended in 120 parts of drylnitrobenzene and the mixture'is stirred for '16 hoiirs :it a. temperature of 193-203 C; It is then filtered hot'andthe solid matter washed and extracted with-boiling dillitephydaioofilorioaacidsfon purification: Adark blufizpniwdei r isalo'htained inwelya good: yield which dlssolvtis':'izrmoncentratedisulfuric "acid: to is}; dull finebnusolutione Analysisshaws; thissproduc tl to.

4.7 parts of finely eminoedibenzaln V 7 hot andthe solid matter "is washed with nitrobenzene, benzene and aloohohendextracted with I 'violet solution. Itflmeltsjat above 460 C. and e 15: be a. Y (4f-benzoylen1ino-lf-anthraquinonyl) 44-17- aniline-1 -anthraquinonyl) -2 8-diaminochrysene of the formula V 1 CHro f a II 2 i Example 2 1 3.25 parts of (4'-benzoylamino-anthraquinonyl)-1':2-amino-8-bromochrysene, made as described in Example 8, 1.8 parts of 4-amino-2- (N)1-benzanthraquinone-acridone, 1.5 parts of calcined sodium carbonate, 1.5 parts of anhydrous sodium acetate and 0.15 part of cuprous chloride are suspended in 70 parts of dry nitrobenzene and the mixture is kept at a temperature of 196-206 C. for 24 hours. It is then filtered hot and the solid matter is washed with nitro-' benzene, benzene and alcohol, and purified by extraction with boiling dilute hydrochloric acid. A blue powder of the formula is thus obtained in good yield which dissolves in concentrated sulfuric acid solution which is at first red-brown and thenolive-brown; it melts at above 460 C. and dyes'cotton green in an olive vat.

-- What we'claimis: 1 J 1 'i 1. A process for the manufacture of derivatives of chrysene, which comprises causing a halogen substituted product of chrysene to react with'a' compound capable of being vatted and containing; at least three condensed six membered carbon rings and at least one 'hydro'gen atorjnf attached to nitrogen, as well' as atfleast one carbonyl group whose carbon atom is a meme berofa six m'emb'er ring. C a H 2'. A process forthe manufacture of derivatives of "chrysene; which comprises causing a dihalog'en substituted product of chrysene toreact with a compound capable of being vatted and containing at least three condensed sixmembered carbon rings and at least one hydrogen atom attached to nitrogen, as well as at least one carbonyl group whose carbon atom is a member of a six-membered ring. 1

4. A process for the manufacture of derivatives of chrysene, which comprises causing 2:8-

dibromo-chrysene to react with a compound capable of being vatted and containing at least three condensed six-membered carbon rings and at least one hydrogen atom attached to nitrogen, as well as at least one carbonyl group whose atom is a member of a six-membered ring.

5. A process for the manufacture of derivatives of chrysene, which comprisesgcausing 1 mol of 2:8-dibromo-chrysene to react with two mols of a compound capable of being vatted and containing at'least three condensed six-membered carbon rings and at least one hydrogen atom attached to nitrogen, as well as at least one carbonyl group whose carbon atom is a member of i -m biedr si 6. Process for the manufacture of derivatives of chrysene, comprising'causing 11 mol of 2: 8- dibrom'o chry'sene to react with 2- mols o'f an' amino-acylamino-anthraquinone. i??? '7. Process for the manufacture of a derivative of chrysene, comprising causing 1 mol of 2:8- dibromo-chrysene' to react with 2 mols of 1- amino-5-benzoylamino-anthraquinone.

8. Process for the manufacture of a derivative of chrysene, comprising causing 1. mol of 2:8- dibromo-chrysene to react with 2 mole of 1- amino-4-benzoylamino-anthraquinone.

9. Process for the manufacture of a derivative of chrysene, comprising causing 1 "mol of 2:8- dibromo-chrysene to react with l mol of l-amino- S-benzoylamino-anthraquinone"and 1 mol of 1- amino-4-benzoy1amino-anthraquinone.

10. Chrysene derivatives of. the formula (R1-NH) nRNH-R2 wherein R stands for a chrysene radical, R1 and R2 each represents a radical of a compound capable of being vatted and containing at least three condensed sixmembered carbon rings and at least one carbonyl group whose carbon atom is a member of a sixmembered carbon ring, and n represents an integer selected from the group consisting of 1, 2 and 3. v

l1. Chrysene derivatives of the formula R1NHR-NHR2 wherein R stands for a chrysene radical, and R1 and R2 each represents I a radical of a compound capable of being vatted and containing at least three condensed sixmembered carbon rings and at least one carbonyl group whose carbon atom is a member of a six-membered carbon ring.

12. Chrysene derivatives of the formula R1-NH-R-NH-R2 wherein R stands for a chrysene radical, and R1 and-R2 each represents a radical of an acylaminoanthraquinone.

13. Chrysene derivatives of the general'formula 10 NH-acyl 14. Chrysene derivatives of the general formula NH-acyl lGQThs clirysene derivative of the formula 17. The chrysene derivative of the formula 18. The chrvsene derivative of the formula I NH-o 0-6 15. Chrysene derivatives of the general formula WALTER'KERQN.

RICHARD TOEBLER. 

